CN112742605A

CN112742605A - Metal ore combined collecting agent and application thereof

Info

Publication number: CN112742605A
Application number: CN202011490146.0A
Authority: CN
Inventors: 刘广义; 孙庆超
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2020-12-16
Filing date: 2020-12-16
Publication date: 2021-05-04

Abstract

The invention belongs to the technical field of metal ore flotation, and particularly discloses a metal ore combined collector which comprises structural substances shown in formulas I, II and III;

R²-S-H formula III. The invention also comprises the flotation application of the combined collector in metal ores, in particular metal sulfide ores. The research of the invention finds that the flotation effect of the sulfide ore can be effectively improved based on the synergy of the formulas I, II and III.

Description

Metal ore combined collecting agent and application thereof

Technical Field

The invention belongs to the technical field of flotation, and particularly relates to the field of metal ore flotation collectors.

Background

Froth flotation is a mineral processing method for separating and purifying useful minerals from ores, and flotation collectors play an important role in froth flotation because of their selective hydrophobicity to valuable mineral particles. At present, the production process of part of flotation collectors has environmental pollution, and needs to be improved urgently, and the characteristics of 'poor, fine and miscellaneous' of mineral resources also require the development of novel flotation collectors and combinations thereof. Therefore, a new flotation collector is developed in a green and economic way, and has an important effect on enriching and recovering metal minerals by a flotation method.

Xanthate is a sulfide flotation collector, douglas W.A (William a douglas, Process of concentrating orders and minerals by flotation, US1943758,1925-2-25) which uses xanthate and halide as raw materials to synthesize xanthate and is used for copper sulfide ore flotation. Norbert and David (Robert B.B., and David E.A. Allyl esterases of alkyl xanthates, U.S. Pat. No. 3, 2808931,1951-5-1) synthesize Allyl xanthates from sodium xanthate and chloropropene, and are used for flotation of copper sulfide ores and zinc sulfide ores. The xanthate has better flotation performance on copper sulfide minerals and copper ion activated zinc sulfide minerals under acidic, neutral and alkaline conditions.

The thionocarbamate is an important sulfide mineral flotation collector, the dosage of which is generally 1/3-1/4 of xanthate, and the thionocarbamate has certain bubble performance. Currently, two processes are usually adopted for preparing thionocarbamate from xanthate, one is that carboxyethyl xanthate is taken as a raw material, and the carboxyethyl xanthate reacts with amine to generate thionocarbamate and thioglycolic acid (preparation of Dynasty. Wangmeisun, gold root and ethionamide. modern chemical industry, 1999,19(1):27-29), and the market limits the production of thionocarbamate due to the byproduct of thioglycolic acid; the other is a hydrocarbyl xanthate starting material which reacts with amines to produce thiourethanes and mercaptans (Harris G.H and Fischback b.c. Process for the manufacture of dialkyl thio carbonates, US2691635,1953-5-20), however, the low carbon number mercaptans (e.g. benzyl mercaptan, amyl mercaptan) are malodorous, pollute the atmosphere, cause significant harm to the human body and cannot be applied to the flotation Process.

Disclosure of Invention

The invention aims to provide a combined collector for metal ores and application thereof in metal ore flotation, aiming at improving the flotation recovery effect of metal useful ores such as copper, molybdenum, nickel, zinc and the like on the basis of composition synergy.

A metal ore combined collector comprises structural substances shown in formulas I, II and III;

R²-S-H formula III

Wherein，R¹Is C₁～C₁₆Any one of hydrocarbon groups; r²Are respectively C₈～C₁₆Any one of hydrocarbon groups; r³Is hydrogen or C₁～C₁₂Any one of hydrocarbon groups; r⁴Is C₁～C₁₂Any one of hydrocarbon groups.

The research of the invention finds that the combination of the formulas I, II and III and the combination control based on the substituent can realize the intramolecular and intermolecular cooperation and effectively improve the flotation effect of the metal ore.

In the present invention, R¹Preferably C₁～C₁₆The alkyl group is more preferably an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, or a n-hexyl group.

The research of the invention discovers that the control R²The substituent groups make the flotation agent suitable for flotation, and improve the synergy of the formulas I, II and III and improve the flotation effect. Preferably, R is²Is a higher alkyl group, preferably C₈～C₁₆Alkyl groups of (a); further preferred is n-octyl, isooctyl, sec-octyl, n-nonyl, n-decyl, p-tert-butylbenzyl, p-isopropylbenzyl, dodecyl or tetradecyl.

R³Hydrogen is preferred.

R⁴Preferably C₁～C₁₂The alkyl group is more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, or a n-hexyl group.

In the combined collecting agent, the molar ratio of the formula I, the formula II and the formula III is 2: 1-20.

The metal ore combined collector is a reaction system (also called as a reaction mixture) for carrying out ammonolysis reaction of a formula I and a formula IV, and comprises a residual raw material of the formula I and ammonolysis products of the formula II and the formula III;

the invention reports that the combined flotation collector with practical value is directly prepared from the high-carbon-number S-alkyl xanthate shown in the formula 1 and the formula IV through aminolysis reaction for the first time. The invention firstly proposes the idea of directly using the reaction systems shown in the formulas 1 and IV as the metal ore flotation collecting agent, and discovers that the flotation application can be successfully realized and the flotation performance can be synergistically improved based on the combined control of the substrates.

Preferably, carrying out ammonolysis reaction on the formula I and the formula IV at the temperature of 30-50 ℃; and acidifying with acid until the pH value is 4.0-7.0 to obtain the combined collector.

Preferably, the combined collector can be prepared by the following method:

carrying out substitution reaction on xanthate shown in a formula V and halogenated hydrocarbon shown in a formula VI to prepare xanthate shown in a formula I; then amine (formula IV) and xanthate (formula I) react to prepare thiourethane and mercaptan shown as II and III, so as to obtain the combined collector.

X-R²Formula VI

Wherein Me is Na⁺Or K⁺(ii) a X represents Cl or Br; r¹Is C₁～C₁₆Any one of hydrocarbon groups; r²Are respectively C₈～C₁₆Any one of hydrocarbon groups; r³Is hydrogen or C₁～C₁₂Any one of hydrocarbon groups; r⁴Is C₁～C₁₂Any one of hydrocarbon groups.

The invention also comprises application of the metal ore combined collector as a collector for flotation of metal ores.

The research of the invention finds that the components have unexpected cooperativity in the aspect of collecting the metal ores, and can improve the flotation effect of the metal ores.

In the invention, the metal ore is metal sulfide ore.

Preferably, the metal ore is a copper sulfide ore, a copper sulfide-molybdenum ore, a copper-lead-zinc ore, a copper-lead ore, a copper-zinc ore, a copper-nickel ore, or a molybdenum sulfide ore.

Preferably, flotation comprises the steps of:

(a) finely grinding metal ores and then performing flotation;

(b) adding a flotation reagent for size mixing in the flotation process, wherein the added reagent at least contains the metal ore combined collecting agent;

(c) useful metal minerals are floated out by a froth flotation method.

Preferably, in the flotation process, the adding amount of the combined collecting agent is 5-150 g/t by taking the weight of the flotation feeding ore as a calculation standard.

Preferably, the pH value of the ore pulp in the flotation process is 5-13.

Advantageous effects

1. The compounds shown in the formulas I, II and III can realize intramolecular and intermolecular synergy based on the control of radicals, and can improve the flotation effect of metal ores;

2. the invention discovers for the first time that the reaction systems shown in the formulas I and IV are directly used as the metal ore flotation collecting agent without separation, so that the treatment process is simplified, and the flotation effect of the metal ore can be improved based on the synergy of the reaction system raw materials and the ammonolysis products. The technical scheme of the invention has no odor, and is a green and efficient flotation collector preparation and application idea.

Drawings

FIG. 1 is a 1HNRM graph of dodecyl isopropyl xanthate;

FIG. 2 is a 1HNRM graph of octyl xanthate isopropyl ester.

Detailed description of the invention

The invention is further illustrated but is not to be limited by the following examples in which parts and percentages are by mass.

Example 1 flotation of chalcopyrite and bornite with a combined collector of dodecyl isopropyl xanthate, ethionamide, dodecanethiol (identified as collector No. 1)

60.9 parts of dodecyl isopropyl xanthate (which is obtained by reacting¹HNRM shown in figure 1) is added into a three-neck reaction bottle, 14.2 parts of 70% ethylamine aqueous solution is added, the mixture reacts for 3 hours at 40 ℃, concentrated sulfuric acid is used for acidification at 5 ℃ until the pH value is about 5, and a water phase is separated to obtain a combined collecting agent of isopropyl xanthate dodecyl ester, ethionamide and dodecyl mercaptan, wherein the molar ratio of the isopropyl xanthate dodecyl ester, the ethioamine and the dodecyl mercaptan in the mixture is 1:4.89:4.89 through ultraviolet detection.

The dosage of the combined collector is 0.2mg/L, the dosage of a foaming agent methyl isobutyl carbinol (MIBC) is 0.2g/L, the pH value is 4-10, and N is₂When the flow rate is 200ml/min, the flotation is respectively carried out for 3 minutes on the bornite and the chalcopyrite with the grain size of 0.076 mm- +0.038, and the recovery rates of the bornite and the chalcopyrite are both higher than 90 percent.

Example 2 flotation of chalcopyrite and bornite with octyl alkyl isopropyl xanthate, propyl thiourethane, octyl mercaptan combined collector (labeled collector No. 2)

60.9 parts of octyl isopropyl xanthate (which is obtained by reacting dimethyl xanthate with dimethyl xanthate) are added¹HNRM shown in figure 2) is added into a three-neck reaction flask, 11.94 parts of propylamine with the purity of 99 percent is added, the mixture reacts for 4 hours at the temperature of 40 ℃, the mixture is acidified to the pH value of about 5 by sulfuric acid at the temperature of 15 ℃, and the water phase is separated to obtain the combined collecting agent of the isopropyl xanthate octyl alkyl ester, the propyl thiourethane and the octyl mercaptan, and the molar ratio of the isopropyl xanthate octyl alkyl ester, the propyl thiourethane and the octyl mercaptan in the mixture is 1:4.43:4.60 through ultraviolet detection.

The dosage of the combined collector is 0.165mg/L, the dosage of a foaming agent methyl isobutyl carbinol (MIBC) is 0.2g/L, the pH value is 4-10, and N is₂When the flow rate is 200ml/min, the flotation is respectively carried out on the bornite and the chalcopyrite with the grain size of 0.076 mm- +0.038 for three minutes, the recovery rate of the bornite is higher than 90 percent, and the recovery rate of the chalcopyrite exceeds 86 percent.

Example 3 flotation of copper sulphide ores

The ore sample of a certain copper-sulfur ore is surrounded in Shangxi, and the raw ore contains 0.52 percent of copper and 7.2 percent of sulfur. The test process comprises the following steps: roughly sweeping, and combining roughly sorted concentrate and swept concentrate; grinding fineness: -0.074mm represents 70%; the medicament conditions are as follows: the dosage of lime is 500 g/ton, the pH value of ore pulp is 8.0, and the other medicament conditions and the results are shown in table 1. The results in table 1 show that the xanthate, thiourethane and mercaptan combined collectors used in the tests achieved higher copper flotation recovery than the collectors such as Z-200, ester-105, dodecyl mercaptan, dodecyl isopropyl xanthate. This is a good indication that the xanthate, thiourethane and thiol combined collectors have excellent collecting properties.

TABLE 1 flotation reagent conditions for copper sulfide ores and results thereof

a, Z-200 is ethionamide; ester-105 is a phosphazenium ester; s-1 is a No. 1 collecting agent; s-2 is the reaction product of dodecyl isopropyl xanthate and propylamine (molar ratio 1: 1); s-3 is No. 2 collector.

Claims

1. The metal ore combined collector is characterized by comprising structural substances shown as formulas I, II and III;

R²-S-H formula III

Wherein R is¹Is C₁～C₁₆Any one of hydrocarbon groups; r²Are respectively C₈～C₁₆Any one of hydrocarbon groups; r³Is hydrogen or C₁～C₁₂Any one of hydrocarbon groups; r⁴Is C₁～C₁₂Any one of hydrocarbon groups.

2. The combined collector for metal ores according to claim 1, wherein R is¹Is C₁～C₁₆Preferably ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl or n-hexyl;

preferably, R²Is C₈～C₁₆Alkyl groups of (a); preference is given to n-octyl, isooctyl, sec-octyl, n-nonyl, n-decyl, p-tert-butylbenzyl, p-isopropylbenzyl, dodecyl or tetradecyl.

3. The combined collector for metal ores according to claim 1, wherein R is³Is hydrogen;

preferably, R⁴Is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl or n-hexyl.

4. The metal ore combined collector according to claim 1, wherein the molar ratio of the formula I, the formula II and the formula III is 2: 1-20.

5. The combined collector for metal ores according to any one of claims 1 to 4, which is a reaction product of an ammonolysis reaction of formula I and formula IV, and comprises a residual raw material of formula I and ammonolysis products of formula II and formula III;

6. the application of the metal ore combined collector as claimed in any one of claims 1 to 5 is characterized in that the metal ore combined collector is used as a collector for flotation of metal ores.

7. The use of a combined collector for metal ores according to claim 6 wherein the metal ores are metal sulphide ores;

8. The use of a combined collector for metal ores according to claim 6 wherein flotation includes the steps of:

(a) finely grinding metal ores and then performing flotation; (b) adding a flotation reagent for size mixing in the flotation process, wherein the added reagent at least contains the metal ore combined collecting agent; (c) useful metal minerals are floated out by a froth flotation method.

9. The use of the combined collector for metal ores according to any one of claims 6 to 8, wherein the combined collector is added in an amount of 5 to 150g/t in terms of the weight of ore fed in the flotation process.

10. The use of the combined collector for metal ores according to any one of claims 6 to 9, wherein the pH of ore pulp in the flotation process is 5 to 13.